Catalyst olefin polymerization and process for olefin polymerization using the same

ABSTRACT

Disclosed are a catalyst for olefin polymerization comprising (A) a compound of a transition metal in Group IVB of the periodic table which contains a ligand having a cyclopentadienyl skeleton, (B) an organoaluminum compound and any one of (C1) a Br.o slashed.nsted acid; (C2) a material obtained by contacting (c-1) a magnesium compound with (c-2) an electron donor; and (C3) a material obtained by contacting (c-1) a magnesium compound, (c-2) an electron donor and (c-3) an organometallic compound with each other. Also disclosed are processes for polymerizing an olefin in the presence of the above-mentioned catalysts for olefin polymerization. Such catalysts and processes for olefin polymerization as described above are excellent in olefin polymerization activity and economical efficiency.

This application is a continuation of application Ser. No. 08/153,371,filed Nov. 16, 1993, abandoned.

FIELD OF THE INVENTION

The present invention relates to a catalyst for olefin polymerizationand a process for olefin polymerization. More particularly, theinvention relates to a Ziegler catalyst for olefin polymerization whichcontains no organoaluminum oxy-compound and to a process for olefinpolymerization using the catalyst.

BACKGROUND OF THE INVENTION

Known in the prior art is a titanium-type catalyst comprising a titaniumcompound and an organoaluminum compound or a vanadium-type catalystcomprising a vanadium compound and an organoaluminum compound, for usein the production of an olefin (co)polymer including an ethylenehomopolymer and ethylene/α-olefin copolymers.

Further, a Ziegler catalyst for olefin polymerization comprising azirconium compound and an organoaluminum oxy-compound (aluminoxane) isalso known as a catalyst which can be used for producing an olefin(co)polymer with a high polymerization activity, and a process forpreparing an ethylene/α-olefin copolymer using such catalyst is proposedin, for example, Japanese Patent Laid-Open Publications No. 19309/1983,No. 35005/1985, No. 35006/1985, No. 35007/1985 and No. 35008/1985.Moreover, a process for polymerizing an olefin using a catalyst formedfrom a mixture of a zirconium compound and an organoaluminum compoundconsisting of aluminoxane and an organoaluminum compound is proposed inJapanese Patent Laid-Open Publications No. 260602/1985 and No.130604/1985.

In the presence of such a catalyst comprising the zirconium compound andthe organoaluminum oxy-compound, olefins can be polymerized with a highpolymerization activity. However, there is such a problem in the case ofusing the organoaluminum oxy-compound that, since the compound isgenerally prepared by causing an organoaluminum compound to react withwater and this reaction process is complicated, the compound becomesexpensive and, therefore, the cost for preparing an olefin (co)polymeralso becomes high.

On that account, eagerly desired now is the advent of a catalyst forolefin polymerization which comprises a zirconium compound and anorganometallic compound other than the organoaluminum oxy-compound andwhich is excellent not only in the olefin polymerization activity butalso in the economical efficiency. Further, the advent of a process forpolymerizing an olefin using such a catalyst is also desired.

As such a catalyst for olefin polymerization, for reference, a catalystcomprising a transition metal compound, a Lewis acid and anorganoaluminum compound is proposed in Japanese Patent Laid-OpenPublication No. 179005/1991.

OBJECT OF THE INVENTION

The present invention has been accomplished to solve the above problemsin the prior art and it is, therefore, an object of the presentinvention to provide a catalyst for olefin polymerization which isexcellent in both the olefin polymerization activity and the economicalefficiency and to provide a process for polymerizing an olefin usingthis catalyst.

SUMMARY OF THE INVENTION

The first catalyst for olefin polymerization according to the presentinvention comprises:

(A) a compound of a transition metal in Group IVB of the periodic table,which contains a ligand having a cyclopentadienyl skeleton;

(B) an organoaluminum compound; and

(C1) a Br.o slashed.nsted acid.

The Br.o slashed.nsted acid (C1) preferably is a solid acid or anorganic acid. The solid acid preferably is an ion-exchange material or aheteropolyacid, and the organic acid preferably is a sulfonic acid.

The second catalyst for olefin polymerization according to the presentinvention comprises:

(A) a compound of a transition metal in Group IVB of the periodic table,which contains a ligand having a cyclopentadienyl skeleton;

(B) an organoaluminum compound; and

(C2) a material obtained by contacting

(c-1) a magnesium compound, with

(c-2) an electron donor.

The third catalyst for olefin polymerization according to the presentinvention is a catalyst for olefin polymerization comprises:

(A) a compound of a transition metal in Group IVB of the periodic table,which contains a ligand having a cyclopentadienyl skeleton;

(B) an organoaluminum compound; and

(C3) a material obtained by contacting with each other

(c-1) a magnesium compound,

(c-2) an electron donor, and

(c-3) an organometallic compound.

The process for olefin polymerization according to the present inventioncomprises polymerizing an olefin in the presence of the above-mentionedcatalysts for olefin polymerization.

The catalyst for olefin polymerization and the process for olefinpolymerization according to the invention are excellent in both theolefin polymerization activity and the economical efficiency.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is an explanatory view of a process for preparing a catalyst forolefin polymerization according to the present invention.

FIG. 2 is an explanatory view of another process for preparing acatalyst for olefin polymerization according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The catalyst for olefin polymerization and the process for olefinpolymerization according to the present invention will be described indetail hereinafter.

The meaning of the term "polymerization" used herein is not limited to"homopolymerization" but may comprehend "copolymerization". Also, themeaning of the term "polymer" used herein is not limited to"homopolymer" but may comprehend "copolymer".

Each of FIGS. 1 and 2 shows steps of a process for preparing thecatalyst for olefin polymerization according to the present invention.

The first catalyst for olefin polymerization according to the presentinvention comprises:

(A) a compound of a transition metal in Group IVB of the periodic table,which contains a ligand having a cyclopentadienyl skeleton;

(B) an organoaluminum compound; and

(C1) a Br.o slashed.nsted acid.

The compound (A) of a transition metal in Group IVB of the periodictable which contains a ligand having a cyclopentadienyl skeleton(hereinafter sometimes referred to as "component (A)") can be a compoundrepresented by following formula (I):

    ML.sub.x                                                   (I)

wherein M is a transition metal selected from metals of Group IVB of theperiodic table; L is a ligand coordinating to the transition metal; atleast one of L is a ligand having a cyclopentadienyl skeleton; L otherthan the ligand having a cyclopentadienyl skeleton is a hydrocarbongroup of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, atrialkylsilyl group, SO₃ R (wherein R is a hydrocarbon group of 1 to 8carbon atoms which may have a substituent group such as halogen), ahalogen atom or hydrogen atom; and x is a valence of the transitionmetal.

In the above formula (I), M is concretely zirconium, titanium orhafnium, and it is preferably zirconium.

Examples of the ligand having a cyclopentadienyl skeleton include acyclopentadienyl group; an alkyl-substituted cyclopentadienyl group,such as a methylcyclopentadienyl group, a dimethylcyclopentadienylgroup, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienylgroup, a pentamethylcyclopentadienyl group, an ethylcyclopentadienylgroup, a methylethylcyclopentadienyl group, a propylcyclopentadienylgroup, a methylpropylcyclopentadienyl group, a butylcyclopentadienylgroup, a methylbutylcyclopentadienyl group and a hexylcyclopentadienylgroup; an indenyl group; a 4,5,6,7-tetrahydroindenyl group; and afluorenyl group. These groups may be substituted with a halogen atom, atrialkylsilyl group, etc.

Of these ligands coordinating to the transition metal, particularlypreferred is an alkyl-substituted cyclopentadienyl group.

When the compound represented by the formula (I) contains at least twogroups each having a cyclopentadienyl skeleton, any optional two of themmay be bonded to each other through an alkylene group such as ethyleneand propylene, a substituted alkylene group such as isopropylidene anddiphenylmethylene, a silylene group, or a substituted silylene groupsuch as dimethylsilylene, diphenylsilylene and methylphenylsilylene.

Examples of the ligand L other than those having a cyclopentadienylskeleton are as follows.

The hydrocarbon group having 1 to 12 carbon atoms includes, for example,an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group.

Concrete examples of the alkyl group include methyl, ethyl, propyl,isopropyl and butyl.

Concrete examples of the cycloalkyl group include cyclopentyl andcyclohexyl. Concrete examples of the aryl group include phenyl andtolyl.

Concrete examples of the aralkyl group include benzyl and neophyl.

The alkoxy group includes, for example, methoxy, ethoxy and butoxy.

The aryloxy group includes, for example, phenoxy.

The halogen includes, for example, fluorine, chlorine, bromine andiodine.

The ligand represented by SO₃ R includes, for example, ap-toluenesulfonate group, a methanesulfonate group and atrifluoromethanesulfonate group.

In case that, for example, the trasition metal has a valence of 4, thetransition metal compound (A) containing a ligand having acyclopentadienyl group is represented more concretely by the followingformula (I'):

    R.sup.1.sub.a R.sup.2.sub.b R.sup.3.sub.c R.sup.4.sub.dM   (I')

wherein M is the same transition metal as that in the formula (I); R¹ isa group (ligand) having a cyclopentadienyl skeleton; R², R³ and R⁴ areeach a group (ligand) having a cyclopentadienyl skeleton, an alkylgroup, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxygroup, an aryloxy group, a trialkylsilyl group, SO₃ R, a halogen atom orhydrogen atom; a is an integer of not less than 1; and a+b+c+d=4.

In the invention, preferably used as the transition metal compound is ametallocene compound represented by the above formula (I') wherein atleast two of R¹, R², R³ and R⁴, for example, R¹ and R², are groups(ligands) each having a cyclopentadienyl skeleton.

The at least two groups (for example, R¹ and R²) each having acyclopentadienyl skeleton may be bonded to each other through analkylene group such as ethylene and propylene, a substituted alkylenegroup such as isopropylidene and diphenylmethylene, a silylene group, ora substituted silylene group such as dimethylsilylene, diphenylsilyleneand methylphenylsilylene.

The other groups (for example, R³ and R⁴) are each a group having acyclopentadienyl group, an alkyl group, a cycloalkyl group, an arylgroup, an aralkyl group, an alkoxy group, an aryloxy group, atrialkylsilyl group, SO₃ R, a halogen atom or hydrogen atom.

Listed below are concrete examples of the transition metal compoundcontaining zirconium as M.

Bis(indenyl)zirconium dichloride,

Bis(indenyl)zirconium dibromide,

Bis(indenyl)zirconiumbis(p-toluenesulfonate),

Bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,

Bis(fluorenyl)zirconium dichloride,

Ethylenebis(indenyl)zirconium dichloride,

Ethylenebis(indenyl)zirconium dibromide,

Ethylenebis(indenyl)dimethylzirconium,

Ethylenebis(indenyl)diphenylzirconium,

Ethylenebis(indenyl)methylzirconium monochloride,

Ethylenebis(indenyl)zirconiumbis(methanesulfonate),

Ethylenebis(indenyl)zirconiumbis(p-toluenesulfonate),

Ethylenebis(indenyl)zirconiumbis(trifluoromethanesulfonate),

Ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,

Isopropylidene(cyclopentadienyl-fluorenyl)zirconium dichloride,

Isopropylidene(cyclopentadienyl-methylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylenebis(cyclopentadienyl)zirconium dichloride,

Dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride,

Dimethylsilylenebis(dimethylcyclopentadienyl)zirconium dichloride,

Dimethylsilylenebis(trimethylcyclopentadienyl)zirconium dichloride,

Dimethylsilylenebis(indenyl)zirconium dichloride,

Dimethylsilylenebis(indenyl)zirconiumbis(trifluromethanesulfonate),

Dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,

Dimethylsilylene(cyclopentadienyl-fluorenyl)zirconium dichloride,

Diphenylsilylenebis(indenyl)zirconium dichloride,

Methylphenylsilylenebis(indenyl)zirconium dichloride,

Bis(cyclopentadienyl)zirconium dichloride,

Bis(cyclopentadienyl)zirconium dibromide,

Bis(cyclopentadienyl)methylzirconium monochloride,

Bis(cyclopentadienyl)ethylzirconium monochloride,

Bis(cyclopentadienyl)cyclohexylzirconium monochloride,

Bis(cyclopentadienyl)phenylzirconium monochloride,

Bis(cyclopentadienyl)benzylzirconium monochloride,

Bis(cyclopentadienyl)zirconium monochloride monohydride,

Bis(cyclopentadienyl)methylzirconium monohydride,

Bis(cyclopentadienyl)dimethylzirconium,

Bis(cyclopentadienyl)diphenylzirconium,

Bis(cyclopentadienyl)dibenzylzirconium,

Bis(cyclopentadienyl)zirconium methoxychloride,

Bis(cyclopentadienyl)zirconium ethoxychloride,

Bis(cyclopentadienyl)zirconiumbis(methanesulfonate),

Bis(cyclopentadienyl)zirconiumbis(p-toluenesulfonate),

Bis(cyclopentadienyl)zirconiumbis(trifluoromethanesulfonate),

Bis(methylcyclopentadienyl)zirconium dichloride,

Bis(dimethylcyclopentadienyl)zirconium dichloride,

Bis(dimethylcyclopentadienyl)zirconium ethoxychloride,

Bis(dimethylcyclopentadienyl)zirconiumbis(trifluoromethanesulfonate),

Bis(ethylcyclopentadienyl)zirconium dichloride,

Bis(methylethylcyclopentadienyl)zirconium dichloride,

Bis(propylcyclopentadienyl)zirconium dichloride,

Bis(methylpropylcyclopentadienyl)zirconium dichloride,

Bis(butylcyclopentadienyl)zirconium dichloride,

Bis(methylbutylcyclopentadienyl)zirconium dichloride,

Bis(methylbutylcyclopentadienyl)zirconiumbis(methanesulfonate),

Bis(trimethylcyclopentadienyl)zirconium dichloride,

Bis(tetramethylcyclopentadienyl)zirconium dichloride,

Bis(pentamethylcyclopentadienyl)zirconium dichloride,

Bis(hexylcyclopentadienyl)zirconium dichloride, and

Bis(trimethylsilylcyclopentadienyl)zirconium dichloride.

In the above-listed examples, the di-substituted cyclopentadienyl ringincludes 1,2- and 1,3-substituted rings and the tri-substitutedcyclopentadienyl ring includes 1,2,3- and 1,2,4-substituted rings. Thealkyl group such as propyl and butyl includes isomers thereof such asn-, i-, sec- and tert-alkyl groups.

In the present invention, compounds in which titanium or hafnium issubstituted for zirconium in the above-exemplified zirconium compoundsmay be used as the transition metal compound (A).

The above-mentioned compounds may be used alone or in combination.Before use, they may be diluted with a hydrocarbon or a halogenatedhydrocarbon.

In the present invention, preferably used as the transition metalcompound (A) is a zirconocene compound having zirconium as the centralmetal atom and containing at least two ligands each having acyclopentadienyl skeleton.

In the present invention, employable as the organoaluminum compound (B)(hereinafter sometimes referred to as "component (B)") is anorganoaluminum compound represented by the following formula (II).

    R.sup.a.sub.n AlX.sub.3-n                                  (II)

wherein R^(a) is a hydrocarbon group of 1 to 12 carbon atoms, X is ahalogen atom or hydrogen atom, and n is 1 to 3.

The hydrocarbon group of 1 to 12 carbon atoms includes, for example, analkyl group, a cycloalkyl group and an aryl group. Concrete examples ofsuch groups include methyl, ethyl, n-propyl, isopropyl, isobutyl,pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl group.Concrete examples of such organoaluminum compound include followingcompounds:

trialkylaluminums such as trimethylaluminum, triethylaluminum,triisopropylaluminum, triisobutylaluminum, trioctylaluminum andtri-2-ethylhexylaluminum;

alkenylaluminums such as isoprenylaluminum;

dialkylaluminum halides such as dimethylaluminum chloride,diethylaluminum chloride, diisopropylaluminum chloride,diisobutylaluminum chloride and dimethylaluminum bromide;

alkylaluminum sesquihalide such as methylaluminum sesquichloride,ethylaluminum sesquichloride, isopropylaluminum sesquichloride,butylaluminum sesquichloride and ethylaluminum sesquibromide;

alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminumdichloride, isopropylaluminum dichloride and ethylaluminum dibromide;and

alkylaluminum hydrides such as diethylaluminum hydride anddiisobutylaluminum hydride.

Also employable as the organoaluminum compound (B) is a compoundrepresented by the following formula (II'):

    R.sup.a.sub.n AlY.sub.3-n                                  (II')

wherein R^(a) is the same as R^(a) in the formula (II); n is 1 or 2; andY is --OR^(b), --OSiR^(c) ₃, --OAlR^(d) ₂, --NR^(e) ₂, --SiR^(f) ₃ or--N(R^(g))AlR^(h) ₂ group.

R^(b), R^(c), R^(d) and R^(h) are each an alkyl group such as methyl,ethyl, isopropyl, isobutyl, cyclohexyl and phenyl groups; R^(e) ishydrogen or a group such as methyl, ethyl, isopropyl, phenyl andtrimethylsilyl groups; and R^(f) and R^(g) are each an alkyl group suchas methyl and ethyl groups.

Concrete examples of such organoaluminum compounds include:

(i) compounds of the formula R^(a) _(n) Al(OR^(b))_(3-n) such asdimethylaluminum methoxide, diethylaluminum ethoxide anddiisobutylaluminum methoxide;

(ii) compounds of the formula R^(a) _(n) Al(OSiR^(c) ₃)_(3-n) such asEt₂ Al(OSiMe₃), (iso-Bu)₂ Al(OSiMe₃) and (iso-Bu)₂ Al(OSiEt₃);

(iii) compounds of the formula R^(a) _(n) Al(OAlR^(d) ₂)_(3-n) such asEt₂ AlOAlEt₂ and (iso-Bu)₂ AlOAl(iso-Bu)₂ ;

(iv) compounds of the formula R^(a) _(n) Al(NR^(e) ₂)_(3-n) such as Me₂AlNEt₂, Et₂ AlNHMe, Me₂ AlNHEt, Et₂ AlN(Me₃ Si)₂ and (iso-Bu)₂ AlN(Me₃Si)₂ ;

(v) compounds of the formula R^(a) _(n) Al(SiR^(f) ₃)₃₋ such as(iso-Bu)₂ AlSiMe₃ ; and

(vi) compounds of the formula R^(a) _(n) Al N(R^(g))--AlR^(h) ₂ !_(3-n)such as Et₂ AlN(Me)--AlEt₂ and (iso-Bu)₂ AlN(Et)Al(iso-Bu)₂.

Further, also employable as the organoalumium compound (B) is an alkylcomplex compound composed of a metal of Group I of the periodic tableand aluminum, which is represented by the following formula:

    M.sup.1 AlR.sup.j.sub.4

wherein M¹ is an alkaline metal such as Li, Na and K, and R^(j) is ahydrocarbon group of 1 to 15 carbon atoms.

Concrete examples of the alkyl complex compound include LiAi(C₂ H₅)₄ andLiAl(C₇ H₁₅)₄.

Of the organoaluminum compounds as exemplified above, preferably usedare trialkylaluminum, dialkylaluminum halide, dialkylaluminum hydrideand dialkylaluminum alkoxide.

The organoaluminum compounds may be used alone or in combination.

The Br.o slashed.nsted acid (C1) (hereinafter sometimes referred to as"component (C1)") used in the present invention includes a solid acidand an organic acid.

The solid acid includes an ion-exchange material and a heteropolyacid.Concrete examples of the ion-exchange material include an ion-exchangeresin, a cellulose ion exchanger and an inorganic ion exchanger.

The ion-exchange resins include a cation-exchange resin and ananion-exchange resin. In the present invention, the cation-exchangeresin, particularly a polystyrene type strongly acidic cation-exchangeresin, is preferably used.

Concrete examples of such polystyrene type cation-exchange resin includea polystyrene type strongly acidic cation-exchange resin such asAmberlyst 15 and Amberlyst 16 (both: trade name) and an ultra-stronglyacidic cation-exchange resin such as Nafion-H (trade name).

As the solid acid, commercially available ones may be per se used, butthey may be pulverized before use because the particle diameter of thesolid acid preferably is as small as possible. The particle diameter ofthe solid acid is preferably not more than 5 mm, more preferably notmore than 2 mm.

Examples of the heteropolyacid including heteropolyacid salts, such asinclude metallic salts or ammonium salts of molybdophosphoric acid,molybdotungstic acid, tungstophosphoric acid, molybdosilicic acid andtungstosilicic acid. Examples of metals for forming the metallic saltsinclude potassium, rubidium, cesium and thallium. Of these, cesium isparticularly preferred.

Concrete examples of such compounds include cesium 12-molybdophosphate,potassium 12-molybdophosphate, rubidium 12-molybdophosphate, thallium12-molybdophosphate and ammonium 12-molybdophosphate.

The organic acid includes carboxylic acids, phenols, sulfonic acids,etc. Sulfonic acids are most preferred. Concrete examples of thesulfonic acids include methanesulfonic acid, ethanesulfonic acid,trifluoromethylsulfonic acid, toluenesulfonic acid, p-toluenesulfonicacid, benzenesulfonic acid and camphor-10-sulfonic acid. Of these,methanesulfonic acid is particularly preferred.

The first catalyst for olefin polymerization according to the presentinvention is formed by contacting the transition metal compound (A), theorganoaluminum compound (B) and the Br.o slashed.nsted acid (C1) witheach other.

The contact of these catalyst components (A), (B) and (C1) may becarried out in an optional order, but it is preferred that theorganoaluminum compound (B) is first fed to the polymerization system,and the transition metal compound (A) and the Br.o slashed.nsted acid(C1) are then fed to the polymerization system to contact these threecomponents with each other.

It is also possible that the Br.o slashed.nsted acid (C1) and theorganoaluminum compound (B) are first mixed to contact them with eachother, followed by contacting with the transition metal compound (A).

When the ion-exchange material is used as the Br.o slashed.nsted acid(C1), the ion-exchange material may be washed with the organoaluminumcompound or the like prior to the contact.

The temperature for contacting the components (A), (B) and (C1) is inthe range of generally -50° to 200° C., preferably -20° to 150° C., andthe period of time therefor is in the range of generally 1 to 3,000minutes, preferably 5 to 1,200 minutes.

Next, the second catalyst for olefin polymerization according to thepresent invention will be described below.

The second catalyst for olefin polymerization according to the presentinvention comprises:

(A) a compound of a transition metal in Group IVB of the periodic table,which contains a ligand having a cyclopentadienyl skeleton;

(B) an organoaluminum compound; and

(C2) a material obtained by contacting

(c-1) a magnesium compound, with

(c-2) an electron donor.

As the compound (A) of a transition metal in Group IVB of the periodictable, which contains a ligand having a cyclopentadienyl skeleton, therecan be exemplified those used for the aforesaid first catalyst forolefin polymerization.

Also as the organoaluminum compound (B), there can be exemplified thoseused for the aforesaid first catalyst for olefin polymerization.

The catalyst component (C2) employable in the present invention is amaterial obtained by contacting a magnesium compound (c-1) with anelectron donor (c-2) both described below.

The magnesium compound (c-1) includes a magnesium compound havingreduction ability and a magnesium compound having no reduction ability.

The magnesium compound having reduction ability is, for example, anorganomagnesium compound represented by the following formula:

    X.sub.n MgR.sub.2-n

wherein R is hydrogen atom, an alkyl group of 1 to 20 carbon atoms, anaryl group or a cycloalkyl group; X is halogen atom; n is a numbersatisfying the relationship of 0<n<2; and when n is 0, two of R may bethe same as or different from each other.

Concrete examples of the organomagnesium compound having reductionability include:

dialkylmagnesium compounds such as dimethyimagnesium, diethylmagnesium,dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium,didecylmagnesium, octylbutylmagnesium and ethylbutylmagnesium;

alkylmagnesium halides such as ethylmagnesium chloride, propylmagnesiumchloride, butylmagnesium chloride, hexylmagnesium chloride andamylmagnesium chloride; alkylmagnesium alkoxides such asbutylethoxymagnesium, ethylbutoxymagnesium and octylbutoxymagnesium; and

other organomagnesium compounds such as butylmagnesium hydride.

Concrete examples of the magnesium compound having no reduction abilityinclude:

magnesium halides such as magnesium chloride, magnesium bromide,magnesium iodide and magnesium fluoride;

alkoxymagnesium halides such as methoxymagnesium chloride,ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesiumchloride and octoxymagnesium chloride;

aryloxymagnesium halides such as phenoxymagnesium chloride andmethylphenoxymagnesium chloride;

alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium,butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium;

aryloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium;and

magnesium carboxylates such as magnesium laurate and magnesium stearate.Also employable as the magnesium compound having no reduction abilityare metallic magnesium and hydrogenated magnesium.

These magnesium compounds having no reduction ability may be compoundsderived from the aforementioned magnesium compounds having reductionability or compounds derived during the preparation stage of a catalystcomponent.

For deriving the magnesium compounds having no reduction ability fromthe magnesium compounds having reduction ability, for example, themagnesium compounds having reduction ability are brought into contactwith polysiloxane compounds, halogen-containing silane compounds,halogen-containing aluminum compounds, esters, alcohols,halogen-containing compounds, or compounds having an OH group or anactive carbon-to-oxygen bond.

The magnesium compounds having reduction ability and the magnesiumcompounds having no reduction ability as described above may be used asa mixture with another metallic compound. These magnesium compounds maybe used singly or in combination. Further, they may be used in a liquidstate or in a solid state.

Of the above-exemplified magnesium compounds, magnesium halide,particularly magnesium chloride, is preferred. The magnesium compoundshaving no reduction ability may be those derived from other materials.

The electron donor (c-2) used in the present invention includes:

oxygen-containing electron donors such as alcohols, phenols, ketones,aldehydes, carboxylic acids, organic acid halides, esters of organic orinorganic acids, ethers, diethers, acid amides, acid anhydrides andalkoxysilanes; and

nitrogen-containing electron donors such as ammonias, amines, nitriles,pyridines and isocyanates.

Concrete examples of the electron donor include:

alcohols having 1 to 18 carbon atoms such as methanol, ethanol,propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol,dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethylalcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol;

halogen-containing alcohols having 1 to 18 carbon atoms such astrichloromethanol, trichloroethanol and trichlorohexanol;

phenols having 6 to 20 carbon atoms which may contain a lower alkylgroup such as phenol, cresol, xylenol, ethylphenol, propylphenol,nonylphenol, cumylphenol and naphthol;

ketones having 3 to 15 carbon atoms such as acetone, methyl ethylketone, methyl isobutyl ketone, acetophenone, benzophenone andbenzoquinone;

aldehydes having 2 to 15 carbon atoms such as acetaldehyde,propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde andnaphthaldehyde;

organic acid esters having 2 to 18 carbon atoms such as methyl formate,methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octylacetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethylvalerate, methyl chloroacetate, ethyl dichloroacetate, methylmethacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methylbenzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octylbenzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyltoluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methylanisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone,δ-valerolactone, coumalin phthallde and ethyl carbonate;

acid halides having 2 to 15 carbon atoms such as acetyl chloride,benzoyl chloride, toluoyl chloride and anisoyl chloride;

ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether,isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole anddiphenyl ether;

acid amides such as N,N-dimethylacetamide, N,N-diethylbenzamide andN,N-dimethyltoluamide;

amines such as trimethylamine, triethylamine, tributylamine,tribenzylamine and tetramethylethylenediamine;

nitriles such as acetonitrile, benzonitrile and trinitrile;

pyridines such as pyridine, methylpyridine, ethylpyridine anddimethylpyridine; and

acid anhydrides such as acetic anhydride, phthalic anhydride and benzoicanhydride.

Preferred examples of the organic acid esters are polycarboxylateshaving a skeleton represented by the following formula: ##STR1## whereinR¹ is a substituted or unsubstituted hydrocarbon group; R², R⁵ and R⁶are each hydrogen atom or a substituted or unsubstituted hydrocarbongroup; R³ and R⁴ are each hydrogen atom or a substituted orunsubstituted hydrocarbon group, preferably at least one of them being asubstituted or unsUbstituted hydrocarbon group; R³ and R⁴ may be bondedto each other to form a cyclic structure; and when the hydrocarbon groupof R¹ through R⁶ is substituted, the substituent group contains aheteroatom such as N, O and S, and has a group such as C--O--C, COOR,COOH, OH, SO₃ H, --C--N--C-- and NH₂.

Examples of such polycarboxylates include aliphatic polycarboxylates,alicyclic polycarboxylates, aromatic polycarboxylates and heterocyclicpolycarboxylates.

Concrete examples of the polycarboxylates preferably used includen-butyl maleate, diisobutyl methylmalonate, di-n-hexylcyclohexenecarboxylate, diethyl nadiate, diisopropyltetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butylphthalate, di-2-ethylhexyl phthalate and dibutyl 3,4-furandicarboxylate.

Phthalates are particularly preferred as the polycarboxylate.

Also employable as the electron donor (c-2) is a compound having atleast two ether linkages existing through a plurality of atoms, which isrepresented by the following formula: ##STR2## wherein n is an integersatisfying the relationship of 2≦n≦10; R¹ to R²⁶ are substituent groupseach having at least one element selected from carbon, hydrogen, oxygen,halogen, nitrogen, sulfur, phosphorus, boron and silicon atom; anyoptional combination of from R¹ to R²⁶, preferably R¹ to R^(2n), mayform in cooperation a ring other than a benzene ring; and an atom otherthan carbon may be contained in the main chain.

Preferred examples of such compound include2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane and2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane.

The above-exemplified electron donors (c-2) may be used in combinationof two or more kinds.

The component (C2) used for the second catalyst for olefinpolymerization according to the present invention is a material obtainedby contacting the magnesium compound (c-1) with the electron donor(c-2). Such component (C2) preferably is a complex formed from themagnesium compound (c-1) and the electron donor (c-2). Of variouscomplexes, preferred is that formed from the magnesium compound (c-1)and alcohol, carboxylic acid or amine. Concrete examples of such complexinclude a magnesium chloride 2-ethylhexyl alcohol complex and amagnesium chloride ethanol complex.

The second catalyst for olefin polymerization according to the presentinvention is formed by contacting the transition metal compound (A)(catalyst component), the organoaluminum compound (B) (catalystcomponent) and the component (C2) with each other. The contact of thecomponent (A), the component (B) and the component (C2) can be carriedout in or outside the polymerization system.

For contacting these components (A), (B) and (C2), it is preferred thatthe component (A) and the component (B) are first contacted with eachother and then they are contacted with the component (C2), or that thecomponent (B) and the component (C2) are first contacted with each otherand then they are contacted with the component (A).

The contact of these components (A), (B) and (C2) may be carried out inthe presence or absence of a solvent. Useful as the solvent arealiphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbonsand halogenated hydrocarbons, which are generally used as polymerizationsolvents.

The temperature for contacting the components (A), (B) and (C2) is inthe range of generally -80° to 200° C., preferably 10° to 150° C., andthe period of time therefor is in the range of generally 0.1 second to10 hours, preferably 1 second to 1 hour.

Next, the third catalyst for olefin polymerization according to thepresent invention will be described below.

The third catalyst for olefin polymerization according to the presentinvention comprises:

(A) a compound of a transition metal in Group IVB of the periodic table,which contains a ligand having a cyclopentadienyl skeleton;

(B) an organoaluminum compound; and

(C3) a material obtained by contacting with each other

(c-1) a magnesium compound,

(c-2) an electron donor, and

(c-3) an organometallic compound.

As the compound (A) of a transition metal in Group IVB of the periodictable, which contains a ligand having a cyclopentadienyl skeleton, therecan be exemplified those used for the aforesaid first catalyst forolefin polymerization.

Also as the organoaluminum compound (B) employable in present invention,there can be exemplified those used for the aforesaid first catalyst forolefin polymerization.

The catalyst component (C3) employable in the present invention is amaterial obtained by contacting a magnesium compound (c-1), an electrondonor (c-2) and an organometallic compound (c-3) with each other.

The magnesium compound (c-1) includes the magnesium compounds having ornot having reduction ability used for the aforesaid second catalyst forolefin polymerization. These magnesium compounds may be used as anorganometallic compound (C-3) described later. Further, the magnesiumcompound may be used as a complex or double compound with another metalsuch as aluminum, zinc, boron, beryllium, sodium and potassium, or as amixture with a compound of a metal such as aluminum, zinc, boron,beryllium, sodium and potassium. The magnesium compounds may be usedsingly or in combination. Further, they may be used in a liquid state orin a solid state.

Of the magnesium compounds, magnesium halide, particularly magnesiumchloride, is preferred. The magnesium compounds having no reductionability may be those derived from other materials.

Useful as the electron donor (c-2) are electron donors used for theaforesaid second catalyst for olefin polymerization.

Useful as the organometallic compound (c-3) are compounds exemplifiedbefore as the organoaluminum compound (B) with respect to the firstcatalyst for olefin polymerization and organometallic compoundscontaining a metal in Group II of the periodic table.

Examples of the organometallic compounds containing a metal in Group IIof the periodic table include a compound represented by the followingformula:

    R.sup.k R.sup.1 M.sup.2

wherein R^(k) is a hydrocarbon group of 1 to 15 carbon atoms or halogenatom, R¹ is a hydrocarbon group of 1 to 15 carbon atoms, and M² is ametal such as Mg, Zn and Cd.

Concrete examples of such compounds include diethylzinc,diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride andbutylmagnesium chloride.

The component (C3) for use in the third catalyst for olefinpolymerization according to the present invention is a material obtainedby contacting the magnesium compound (c-1), the electron donor (c-2) andthe organometallic compound (c-3) with each other. Concretely, there canbe mentioned, as the component (C3), a material obtained by bringing acomplex formed from the magnesium compound (c-1) and the electron donor(c-2) into contact with the organometallic compound (c-3), and amaterial obtained by bringing the magnesium compound (c-1), the electrondonor (c-2) and the organometallic compound (c-3) into contact with eachother.

The contact of the complex formed from the magnesium compound (c-1) andthe electron donor (c-2) with the organometallic compound (c-3), or thecontact of the magnesium compound (c-1), the electron donor (c-2) andthe organometallic compound (c-3) with each other can be carried out inan organic solvent. Useful as the organic solvent are aliphatichydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and thehalogenated hydrocarbons, which are generally used for polymerization.

In the contact of the complex formed from the magnesium compound (c-1)and the electron donor (c-2) with the organometallic compound (c-3), theorganometallic compound (c-3) is used preferably in an amount of 0.1 to1,000 times by mol the amount of the complex. In this case, thetemperature for the contact is in the range of generally -70° to 200°C., preferably 10° to 150° C., and the period of time therefor is in therange of generally 0.1 second to 10 hours, preferably 1 second to 1hour.

The third catalyst for olefin polymerization according to the presentinvention is formed by contacting the transition metal compound (A)(catalyst component), the organoaluminum compound (B) (catalystcomponent) and the component (C3) with each other. The contact of thesecomponents (A), (B) and (C3) may be carried out in or outside thepolymerization system.

The contact of these components (A), (B) and (C3) may be carried out inan optional order, but it is preferred that the component (A) and thecomponent (B) are first contacted with each other and then they arecontacted with the component (C3), or that the component (B) and thecomponent (C3) are first contacted with each other and then they arecontacted with the component (A). Of these, particularly preferred isthat the component (A) and the component (B) are first contacted witheach other and then they are contacted with the component (C3).

The contact of these components (A), (B) and (C3) may be carried out inthe presence or absence of a solvent. Useful as the solvent arealiphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbonsand halogenated hydrocarbons, which are generally used as polymerizationsolvents.

The temperature for contacting the components (A), (B) and (C3) is inthe range of generally -80° to 200° C., preferably 10° to 150° C., andthe period of time therefor is in the range of generally 0.1 second to10 hours, preferably 1 second to 1 hour.

The catalysts for olefin polymerization according to the presentinvention described hereinbefore may contain other components which areuseful for olefin polymerization in addition to the above-describedcomponents.

Use of the catalysts for olefin polymerization according to the presentinvention makes it possible to polymerize an olefin with a highpolymerization activity.

In the process for olefin polymerization according to the presentinvention, an olefin is polymerized in the presence of theabove-described catalysts for olefin polymerization.

Examples of olefins employable in the polymerization includes α-olefinshaving 2 to 20 carbon atoms such as ethylene, propylene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

Also employable are cyclopentene, cycloheptene, norbornene,5-methyl-2-norbornene, tetracyclododecene,2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,styrene, vinylcyclohexane, dienes, etc.

With respect to the first catalyst for olefin polymerization, thecomponent (A) is used in the polymerization in an amount of usually0.00001 to 10.0 mmol, preferably 0.0001 to 0.1 mmol, in terms of thetransition metal atom contained in the transition metal compound (A),per 1 liter of the polymerization volume.

The organoaluminum compound (B) is used in an amount of usually 0.008 to800 mmol, preferably 0.008 to 8 mmol, in terms of the aluminum atomcontained in the organoalumium compound (B), per 1 liter of thepolymerization volume.

In the case of using an ion-exchange material as the Br.o slashed.nstedacid (C1), the ion-exchange material is used in an amount of usually0.0001 to 1,000 mmol equivalent, preferably 0.001 to 10 mmol equivalent,in terms of ion-exchange equivalent.

In the polymerization, the organoaluminum compound (B) is used in suchan amount that the gram atom ratio (Al/transition metal) of the aluminumatom contained in the compound (B) to the transition metal contained inthe transition metal compound (A) is in the range of usually 0.5 to10,000, preferably 2 to 1,000. When the Br.o slashed.nsted acid (C1) isan ion-exchange material, the ion exchange material is used in such anamount that the ratio (eq/transition metal) of the ion exchangeequivalent of the compound (C1) to the transition metal gram atomcontained in the transition metal compound (A) is in the range ofusually 0.5 to 1,000, preferably 1 to 100.

With respect to the second and third catalysts for olefinpolymerization, the component (A) is used in the polymerization in anamount of usually 0.0001 to 10.0 mmol, preferably 0.001 to 5.0 mmol, interms of the transition metal atom contained in the component (A), per 1liter of the polymerization volume.

The component (B) is used in an amount of usually 0.008 to 800 mmol,preferably 0.08 to 80 mmol, in terms of the aluminum atom contained inthe component (B), per 1 liter of the polymerization volume.

The component (C2) or the component (C3) is used in an amount of usually0.0001 to 1,000 mmol, preferably 0.001 to 100 mmol, in terms of themagnesium atom contained in the component (C2) or the component (C3),per 1 liter of the polymerization volume.

In the polymerization, the component (B) is used in such an amount thatthe gram atom ratio (Al/M) of the aluminum atom (Al) contained in thecomponent (B) to the transition metal (M) contained in the component (A)is in the range of usually 1 to 10,000, preferably 1 to 1,000.

The component (C2) or the component (C3) is used in such an amount thatthe gram atom ratio (Mg/M) of the magnesium atom (Mg) contained in thecomponent (C2) or the component (C3) to the transition metal (M)contained in the component (A) is in the range of usually 0.5 to 1,000,preferably 1 to 100.

In the present invention, the polymerization may be conducted by aprocess for liquid phase polymerization such as suspensionpolymerization or by a process for gas phase polymerization.

When the polymerization is conducted by a process for liquid phasepolymerization, hydrocarbons may be used as a polymerization solvent.Examples of the hydrocarbons include:

aliphatic hydrocarbons such as propane, butane, pentane, hexane,heptane, octane, decane, dodecane and kerosine;

alicyclic hydrocarbon such as cyclopentane, cyclohexane andmethylcyclopentane;

aromatic hydrocarbons such as benzene, toluene and xylene; and

halogenated hydrocarbons such as ethylene chloride, chlorobenzene anddichloromethane. These hydrocarbons may be used singly or incombination. Further, the olefin itself may be used as a solvent.

The temperature for the olefin polymerization is in the range of usually-50° to 150° C., preferably 0° to 100° C. The polymerization pressure isin the range of usually atmospheric pressure to 100 kg/cm², preferablyatmospheric pressure to 50 kg/cm².

The polymerization may be carried out either batchwise,semi-continuously or continuously. Further, the polymerization may becarried out in two or more steps having reaction conditions differentfrom each other.

The molecular weight of the olefin polymer to be obtained can beregulated by allowing hydrogen to exist in the polymerization system orby changing the polymerization temperature.

With respect to the catalysts for olefin polymerization according to thepresent invention, the aforementioned catalyst components may beprepolymerized with an olefin.

EFFECT OF THE INVENTION

By the use of the catalyst for olefin polymerization according to thepresent invention, an olefin can be polymerized with a highpolymerization activity even if any organoaluminum oxy-compound is notused. Further, the catalyst for olefin polymerization according to thepresent invention is available at a low cost because an expensiveorganoaluminum oxy-compound is not used.

In the process for olefin polymerization according to the presentinvention, an olefin polymer can be prepared at a high yield andeconomically because an olefin is polymerized in the presence of theabove-mentioned catalyst.

EXAMPLE

The present invention will be described below in more detail withreference to examples, but it should be construed that the presentinvention is in no way limited to those examples.

EXAMPLE 1

A glass polymerizer thoroughly purged with nitrogen was charged with1,000 ml of purified toluene. The polymerizer was warmed to 75° C., andethylene was introduced into the polymerizer to sufficiently saturatetoluene with ethylene. Thereafter, to the polymerizer were successivelyadded 0.75 mmol (in terms of aluminum atom) of triisobutylaluminum as atoluene solution, 0.005 mmol (in terms of zirconium atom) ofethylenebis(indenyl)zirconium dichloride as a toluene solution and 62.5mg 0.05 mmol equivalent in terms of --SO₂ OH group! of an ultra-stronglyacidic ion-exchange resin (trade name: Nafion-H), to initiatepolymerization. After 20 minutes, a small amount of isobutyl alcohol wasadded to terminate the polymerization. Then, a polymer was precipitatedin the whole amount by the use of a large amount of methanol, followedby adding a small amount of hydrochloric acid. The resultant mixture wasfiltered over a glass filter to collect the polymer and the polymer waswashed with methanol.

The polymer was dried at 80° C. for 10 hours under a reduced pressure,to obtain 12.95 g of polyethylene.

The polyethylene thus obtained had an intrinsic viscosity η!, asmeasured in decalin at 135° C., of 1.84 dl/g.

Comparative Example 1

The procedure of Example 1 was repeated except for not using theultra-strongly acidic ion-exchange resin (Nafion-H), to performpolymerization. As a result, 5.85 g of polyethylene was obtained.

The polyethylene thus obtained had an intrinsic viscosity η! of 1.71dl/g.

EXAMPLE 2

The procedure of Example 1 was repeated except for using 11.3 mg 0.05mmol equivalent in terms of --SO₂ OH group! of a cation-exchange resin(trade name: Amberlist 15E) in place of the ultra-strongly acidicion-exchange resin (Nafion-H) and using 0.4 mmol (in terms of aluminumatom) of the toluene solution of triisobutylaluminum, to performpolymerization. As a result, 11.9 g of polyethylene was obtained.

EXAMPLE 3

A glass polymerizer thoroughly purged with nitrogen was charged with1,000 ml of purified toluene. The polymerizer was warmed to 75° C., andethylene was introduced into the polymerizer to sufficiently saturatetoluene with ethylene.

Separately, to a 20 ml Schrenk bottle were added 22.5 mg 0.1 mmolequivalent in terms of -SO₂ OH group! of a cation-exchange resin (tradename: Amberlist 15E) and 5.0 ml of toluene, and then further added 0.2mmol (in terms of aluminum atom) of a toluene solution oftriisobutylaluminum. The resultant mixture was stirred at roomtemperature for 10 minutes.

Then, to the above polymerizer were successively added 0.2 mmol (interms of aluminum atom) of triisobutylaluminum and 0.005 mmol (in termsof zirconium atom) of ethylenebis(indenyl)zirconium dichloride, and wasfurther added all the reaction solution obtained in the Schrenk bottleto initiate polymerization. After 20 minutes, a small amount of isobutylalcohol was added to terminate the polymerization. Then, a posttreatment was carried out in the same manner as described in Example 1,to obtain 16.0 g of polyethylene.

EXAMPLE 4

The procedure of Example 3 was repeated except for using 27.3 mg 0.12mmol equivalent in terms of --SO₂ OH group! of the cation-exchange resin(trade name: Amberlist 15E) having been ground in a mortar, to performpolymerization. As a result, 22.05 g of polyethylene was obtained.

EXAMPLE

The procedure of Example 3 was repeated except for usingtridecylaluminum in place of the triisobutylaluminum and varying thepolymerization period to 45 minutes, to perform polymerization. As aresult, 16.48 g of polyethylene was obtained.

Comparative Example 2

The procedure of Example 4 was repeated except for not using thecation-exchange resin, to perform polymerization. As a result, 6.30 g ofpolyethylene was obtained.

EXAMPLE 6

The procedure of Example 1 was repeated except for varying the amount ofthe ethylenebis(indenyl)zirconium dichloride to 0.002 mmol and using0.02 mmol (in terms of phosphorus atom) of cesium 12-molybdophosphate inplace of the ultra-strongly acidic cation-exchange resin (Nafion-H), toperform polymerization. As a result, 5.88 g of polyethylene wasobtained.

EXAMPLE 7

The procedure of Example 1 was repeated except for using 0.05 mmol ofmethanesulfonic acid in place of the ultra-strongly acidiccation-exchange resin (Nafion-H), to perform polymerization. As aresult, 12.2 g of polyethylene was obtained.

EXAMPLE 8

Preparation of a component (c-i)!

95.2 g of magnesium chloride anhydride, 442 ml of decane and 390.6 g of2-ethylhexyl alcohol were reacted with each other at 130° C. for 2 hoursto give a homogeneous solution (component (c-i)).

Polymerization!

A glass polymerizer purged with nitrogen was charged with 1,000 ml oftoluene, then the polymerizer was warmed to 75° C., and ethylene wasintroduced into the polymerizer. Then, to the polymerizer were addedtriisobutylaluminum (0.4 mmol in terms of aluminum atom) and thecomponent (c-i) (0.05 mmol in terms of magnesium atom). After 2 minutes,to the polymerizer was further added ethylenebis(indenyl)zirconiumdichloride (0.005 mmol in terms of zirconium atom) to initiatepolymerization. After the polymerization was performed for 30 minutes, asmall amount of isobutyl alcohol was added to terminate thepolymerization. The reaction product was introduced into a large amountof methanol to precipitate a polymer in the whole amount. To theprecipitated polymer was added a hydrochloric acid, and the resultantmixture was filtered over a glass filter to collect the polymer. Thepolymer was dried for 10 hours under vacuum, to obtain 9.75 g ofpolyethylene. The polyethylene thus obtained had an intrinsic viscosityη! of 1.66 dl/g.

EXAMPLE 9

The procedure of Example 8 was repeated except for varying the additionorder of the catalyst components to the polymerizer so that thetriisobutylaluminum and the ethylenebis(indenyl)zirconium dichloridewere first added and after 2 minutes the component (c-i) was furtheradded, to perform polymerization. As a result, 1.48 g of polyethylenewas obtained. The polyethylene thus obtained had an intrinsic viscosityη! of 1.69 dl/g.

Comparative Example 3

The procedure of Example 8 was repeated except for varying the additionorder of the catalyst components to the polymerizer so that thecomponent (c-i) and the ethylenebis(indenyl)zirconium dichloride werefirst added and after 2 minutes the triisobutylaluminum was furtheradded, to perform polymerization. As a result, 0.93 g of polyethylenewas obtained.

EXAMPLE 10

Preparation of a solution of a component (c-ii)!

To a toluene solution of magnesium chloride 3-ethylhexyl alcohol complex(26.4 mmol) was dropwise added a toluene solution of triisobutylaluminum(92.4 mmol) while stirring, to prepare a solution of a component (c-ii).

Polymerization!

A glass polymerizer purged with nitrogen was charged with 1,000 ml oftoluene, then the polymerizer was warmed to 75° C., and ethylene wasintroduced into the polymerizer. Then, to the polymerizer were addedtriisobutylaluminum (0.4 mmol in terms of aluminum atom) and thesolution of a component (c-ii) (0.5 mmol in terms of magnesium atom).After 2 minutes, to the polymerizer was further addedethylenebis(indenyl)zirconium dichloride (0.005 mmol in terms ofzirconium atom) to initiate polymerization. After the polymerization wasperformed for 60 minutes, a small amount of isobutyl alcohol was addedto terminate the polymerization. The reaction product was introducedinto a large amount of methanol to precipitate a polymer in the wholeamount. To the precipitated polymer was added a hydrochloric acid, andthe resultant mixture was filtered over a glass filter to collect thepolymer. The polymer was dried for 10 hours under vacuum, to obtain11.30 g of polyethylene. The polyethylene thus obtained had an intrinsicviscosity η! of 1.91 dl/g.

EXAMPLE 11

The procedure of Example 10 was repeated except for using the solutionof a component (c-ii) in an amount of 0.05 mmol in terms of magnesiumatom, to perform polymerization. As a result, 42.30 g of polyethylenewas obtained. The polyethylene thus obtained had an intrinsic viscosityη! of 2.34 dl/g.

EXAMPLE 12

The procedure of Example 10 was repeated except for using the solutionof a component (c-ii) in an amount of 0.015 mmol in terms of magnesiumatom, to perform polymerization. As a result, 48.25 g of polyethylenewas obtained. The polyethylene thus obtained had an intrinsic viscosityη! of 2.40 dl/g.

EXAMPLE 13

The procedure of Example 10 was repeated except for usingtridecylaluminum in place of the triisobutylaluminum, to performpolymerization. As a result, 43.20 g of polyethylene was obtained. Thepolyethylene thus obtained had an intrinsic viscosity η! of 2.46 dl/g.

EXAMPLE 14

Preparation of a suspension of an Al-free component (c-iii)!

A glass reactor was equipped with a cooling tube, a dropping funnel anda stirring bar, and the reactor placed on an oil bath was purged withnitrogen. The reactor were charged with toluene and MGCl₂.2.61 C₂ H₅ OH(25 mmol) in a nitrogen atmosphere, and to the reactor was then dropwiseadded slowly triisobutylaluminum (75 mmol) while stirring the content ofthe reactor. Thereafter, the temperature of the oil bath was elevated to80° C. to perform reaction for 1 hour. After completion of the reaction,a solid was filtered over a glass filter in a nitrogen atmosphere andwashed with toluene. The solid was suspended again in toluene, toprepare a suspension of an Al-free component (c-iii).

Polymerization!

The polymerization procedure in Example 10 was repeated except for usingthe suspension of an Al-free component (c-iii) (0.05 mmol in terms ofmagnesium atom) in place of the solution of a component (c-ii), toperform polymerization. As a result, 10.2 g of polyethylene wasobtained.

EXAMPLE 15

The procedure of Example 14 was repeated except for varying the additionorder of the catalyst components to the polymerizer so that thetriisobutylaluminum and the ethylenebis(indenyl)zirconium dichloridewere first added and after 2 minutes the suspension of an Al-freecomponent (c-iii) was further added, to perform polymerization. As aresult, 5.63 g of polyethylene was obtained.

EXAMPLE 16

The procedure of Example 14 was repeated except for using the suspensionof an Al-free component (c-iii) in an amount of 0.4 mmol in terms ofmagnesium atom, to perform polymerization. As a result, 4.75 g ofpolyethylene was obtained.

EXAMPLE 17

The procedure of Example 14 was repeated except for using the suspensionof an Al-free component (c-iii) in an amount of 0.015 mmol in terms ofmagnesium atom, to perform polymerization. As a result, 11.0 g ofpolyethylene was obtained.

What is claimed is:
 1. A process for olefin polymerization comprisingpolymerizing an olefin in the presence of a catalyst for olefinpolymerization comprising:(A) a compound of a transition metal in GroupIVB of the Periodic Table, which is represented by the following formula(I'):

    R.sup.1.sub.a R.sup.2.sub.b R.sup.3.sub.c R.sup.4.sub.d M

wherein M is zirconium; R¹ is a ligand having a cyclopentadienylskeleton; R², R³ and R⁴ are each a ligand having a cyclopentadienylskeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkylgroup, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO₃ R(wherein R is a hydrocarbon group of 1 to 8 carbon atoms or asubstituted hydrocarbon group of 1 to 8 carbon atoms), a halogen atom orhydrogen atom, a is an integer of not less than 1; and a+b+c+d=4, andwherein at least one of R², R³ and R⁴ is the ligand having thecyclopentadienyl skeleton; (B) an organoaluminum compound; and (C) aBr.o slashed.nsted acid which is a polystyrene strongly acidiccation-exchange resin having SO₂ OH groups.
 2. The process of claim 1wherein olefin is polymerized in the presence of a catalyst comprisingthe transition metal compound (A) in an amount of from about 0.00001 to10 mmol per liter of polymerization volume, the organoaluminum compound(B) in an amount of from about 0.008 to 800 mmol per liter ofpolymerization volume, and the Br.o slashed.nsted acid (C) in an amountof about 0.0001 to 1,000 mmol in terms of ion exchange equivalent. 3.The process of claim 1 wherein olefin is polymerized in the presence ofa catalyst wherein the ratio of the amount of polystyrenecation-exchange resin (C) to the amount of the transition metal compound(A) is in the range of from about 0.5 to 1,000, in terms of ion exchangeequivalent of the compound (C) to the metal gram atom of the transitionmetal.